Cleaning compositions containing softeners



United States Patent 6 ice 3,336,770

Patented July 11, 1967 3 330 770 cleaning textile materials, as forexample, in a laundering CLEANlNG COMPbSI'i'IONS CONTAINING operation,result in superior absorbency rating when com- SOE'IENERS pared withother known softeners, regardless of their William Julius van Loo, J12,Middlesex, George Robert De method of employment.

Paolo, Readington Township, Hunterdon County, and 5 These and otherobjects and advantages of the present Samuel James Ollrieu, Dunellen,N.J., assigno t0 invention will become apparent from the detaileddescrip- Amelllcall cyfihfimld Company, Stamford, -a a tion thereof setforth hereinbelow. poration of Maine u According to the presentinvention, a cleaning com- No g i gg 338292 position is providedcomprising a detergent selected from 10 the group consisting of anionicand non-ionic types and This invention relates to cleaning compositionsand to an acid salt of a composition of matter containing as the the useof such compositions on various substrates, as desired component a baseof the following structure:

for example, on textile materials, human hair, and the wherein R is analkyl group of from 12 to 22 carbon like. More particularly, the presentinvention relates to atoms, inclusive, where x is selected from thegroup condetergent-softener cleaning compositions and to the use sistingof 1 and 2, y is a small integer of from 0 to 3, of such compositions inthe cleaning of various substrates and where A is selected from thegroup consisting of O such as are identified above. and S. 3

At the present time there are commercially available It has beendiscovered that the salts of the bases set a number of softening agentswhich may be employed at forth above can be employed in combination withanionic an appropriate interval in various cleaning operations or andnon-ionic detergents to produce a high degree of softprocedures, as forexample, in home or commercial washness without affecting the waterabsorbency of laundered ing equipment for imparting softness to thewashed or textile materials. This unique advantage is whollyunoblaundered material. vious in view of the fact that the salts arecationic and Typical of such softeners are those identified as 1) wouldnot be expected to be compatible with the anionic solutions ofquaternary ammonium alts, (2) olid ur detergent. This constitutes anadvance long sought by adducts of the same general chemical type, and(3) emuldetergent manufacturers and others interested in provid sions ofpolyethylene. The first type, when used in the ingtextile agents andauxiliaries final rinse cycle of a washer, may be highly effective as ASnoted above, R is all alkyl g p of from 12 f0 22 softeners, dependingupon the particular substituents f carbon atoms which can be straight orbranched chained the quaternary ammonium salt. However, these are i andsaturated or unsaturated. Dodecyl, tn'decyl, pentaeffective andincompatible when employed in the presence y heptadecyl, octfldecyl,eicosyl, heheicosyl, p of anionic detergents. Softeners of the secondand third y J p y and SJLM-hePtfldeCatIieHYI types have also been foundnot to be compatible with are examples of Such alkyl groups, theheptadecyl P anionic detergents and when used in the wash cycle of abeing Preferred for economic reasonshome automatic washer do not producea significant level The bases Salt Precursors are reaction Products ofsoftness to the textile materials, particularly cellulosic 0f 1 mole ofa fatty acid of the amide of nd 1 at i l 7 mole of a polyethylenepolyamine of the general formula In addition to the cited disadvantagesof the softeners 2( 2 2 )m Where m is 2 the reaction referred to above,their use normally adversely affects the being carried out at for hoursat atmospheric P absorbency of the substrate softened. In the case oftowels Sure and a temperature of from to (P and other articles formed oftextile material for which erahly to effect the removal of Z absorbencyis important, this is a definite disadvantage. moles of Water where theacid is p y 0f 1 111016 Amordingly, it is an object f the presentinvention to each of water and ammonia where the amide is employedprovide novel deaning compositions, Particularly those and subsequentcondensation to form a 1,2-substituted containing a detergent and asoftener which are compatiimidazohne ble in use, thereby permittingtheir simultaneous use with R the avoidance of the necessity for anadditional softening step in the cleaning process, as for example, inhome or f commercial laundering or in shampooing various sub- N T Tstrates, such as rugs, slipcovers, or human hair. 011E051 m It is afurther object of the present invention to prowhere m is 1 or 2. Therefollows a heat ageing treatment vide such cleaning compositions whichwhen employed in for an additional 614 hours, and preferably 8-12 hours,

which effects a change in the product when the acid is the startingmaterial, the nature of the change is presently unknown but transformsthe resulting material from one capable of yielding an inadequate fabricsoftener to one capable of forming an exceptionally effective softenerwhen employed in the presence of a synthetic detergent.

Such heat ageing is unnecessary where the amide is employed as thestarting material.

The said base is then preferably but not necessarily crosslinked with acompound of the formula where n is 1 or 2 and A is O or S to form acompound of the type represented by Formula I above and subsequentlysaid compound is converted to the acid salt by reaction with an acid.

It should be noted that the structure given (I) is that of the desiredreaction product but that such product is not formed exclusively by thepreparation process given. A number of side reaction products arepossible and are formed, some of which may not contribute to thesoftening effect observed. By careful control of the various steps inthe reaction, however, a successfully performing product is obtained,indicating a favorable concentration of the desired material.

To convert the base to a salt, typically a solution of about 2.5% to 15%or more of solids of the base is prepared in aqueous medium at a pHrange of from 2.5 to about 6 or higher by the addition of various acids,whether they be organic or inorganic. Typically, such acids includeacetic, lactic, tartaric, citric, formic, boric, oxalic, benzoic,phosphoric, sulfuric, methylsulfuric and the like. Alternatively, thebase may be melted with the required amount of appropriate acid to formthe salt, subsequently cooled and pulverized to form a dry product.

As noted above, the detergents may be anionic or nonionic.

The anionic detergents which may be used in the compositions of thisinvention include alkali metal fatty acid soaps and in addition the wellknown surface active alkali metal sulfonates and sulfates. The lattergroup may be employed as the sole detergent base or in admixture withalkali metal fatty acid soaps, as for. example, 1 part of fatty acidsoap to 0.5 to 2 parts by weight of surface active alkali metalsulfonates or sulfates or mixtures thereof. A preferred group of thisclass is the long chain alkyl or alkaryl sulfonates, i.e., those whereinthe alkyl group is straight or branched in structure, and contains from8 to 22 carbon atoms but preferably 10 to 16 carbon atoms, examples ofwhich are octyl, decyl, dodecyl, pentadecyl, hexadecyl, octadecyl, mixedlong chain alkyl derived from long chain fatty acids such as the laurylradical, cracked paraffin wax olefins, polymers of low mono-olefins suchas propylene tetramer and the like, and wherein the aryl radical isderived from benzene, toluene, xylene, phenol, the cresols, naphthaleneand the like. Specific examples of such surface active agents includesodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodiumlaurylbenzenesulfonate, and sodium hexadecylbenzenesulfonate. Othersulfonate surface active agents are contemplated also, as for example,the long chain alkyl sulfonates such as sodium hexadecylsulfonate andsodium octadecylsulfonate.

The well-known sulfate detergents having 8 to 26 carbon atoms andparticularly those having an alkyl radical of about 12 to 22 carbonatoms may be employed as an anionic detergent in the compositions of ourinvention. Such detergents include sulfuric acid esters of polyhydricalcohols incompletely esterified with fatty acids, e.g., sodium tallowdiglyceride monosulfate, the pure and mixed alkyl sulfates, and highersulfates such as sodium lauryl sulfate and sodium cetyl sulfate.

Additional anionic surface active sulfonates and sulfates contemplatedby this invention are the sulfonated and sulfated alkyl acid amides suchas Igepon T of the formula The sulfated and sulfonated esters such asIgepon AT of the formula RCOOCH SO Na in which R is an alkyl radicalcontaining from 12 to 18 carbon atoms, the sodium salt of the sulfonicacid derivative of an aliphatic dialkyl dicarboxylate, disodiumsulfosuccinate such as and the like are also contemplated.

In addition to the anionic surface active agents, nonionic surfaceactive agents may be used as the base for the compositions of ourinvention. The non-ionic surface active agents which may be used areviscous liquid, wax-like, water-soluble surface active substancescontaining a polyglycol ether group of the structure in which Z and Zare hydrogen or short chain alkyl, p is an integer greater than 3 and Zis a residue of a monomeric organic compound having an active hydrogen,as for example, an alcohol, a phenol, an amide, a secondary amine, acarboxylic acid or the like. These non-ionic detergents are well known(e.g., U.S.P. 1,970,578 and U.S.P. 2,213,477) and may be typified bypolyalkylene oxide derivatives (e.g., polyethylene oxide, polypropyleneoxide, polybutylene oxide) of water-insoluble higher fatty acids, suchaslauric, oleic, palmitic, and stearic and the like or mixtures thereofsuch as the mixture of fatty acids obtained from animal and vegetablefats and oils and by the oxidation of petroleum fractions such asparafiin wax. They may also be exemplified by the polyalkylene oxidederivatives of such water-insoluble organic hydroxy compounds as higheraliphatic alcohols (i.e., the alcohols corresponding to the fatty acidsspecified above or mixtures thereof), phenols, particularly alkylphenols, containing at least 6 alkyl carbon atoms such as isooctyl,di-t-butyl, tri-isopropyl, nonyl, dodecyl, octadecyl phenols ornaphthols, or of aralkyl alcohols such as benzyl alcohol, cinnamylalcohol and the like. They may also be exemplified by the polyalkyleneoxide derivatives of such amines as stearyl, lauryl, dicyclohexyl,dibutyl amine and the like. A particularly useful non-ionic detergent isthat obtained by condensing 1 mole of tall oil with 5-15 moles ofethylene oxide.

In aqueous laundering conditions, the laundering medium will containfrom about .00005% to about 1% and preferably from about .0001% to about.5 of detergent and from .00005% to about .1% and preferably from .000l%to 01% of softener as the salt.

Laundering mediums of the type described above will contain from .0002to about 2% and preferably from .002 to .2% of softener as the saltbased on the dry weight of the substrate such as the textile material isto be laundered.

For formulated softener-detergent compositions, whether they be solid,as for example powdered or formed in bars, or liquid, it has been foundthat the amount of softener by weight in the complete formulation willvary widely, i.e., from about 1% to about 50% depending upon therecommended use concentrations of the formulation. For most cleaningcompositions, however, the range of softener by weight based on theweight of a complete formulation will be from about 5 to about 30%.

Expressed in parts by weight detergent compositions comprising from 5 toparts of a detergent selected from the group consisting of anionic andnon-ionic detergents and from about 0.1 to about 20 parts of thesoftener are contemplated.

The amount of active detergent substituent in the cleaning compositionwill vary within wide limits and will depend upon such factors as thenature of the detergent itself as well as other constituents present inthe composition. It has been found that from about 5 to about 30% of thetotal weight of such compositions may advantageously be the detergentconstituent with the preferred narrower commercial limits being fromabout to about The cleaning composition may also have added to itvarious other special additives depending upon the particular end useand physical form in which it is to be employed. Thus, detergentformulations of the type employable as powders may contain hydrotropesor coupling agents, building agents and fillers including soda ash,sodium sesquicarbonate, sodium tetrapyrophosphate, sodiumtripolyphosphate, sodium silicate, sodium metasilicate, borax, and thelike. In addition, non-alkaline inorganic salts such as sodium sulfate,sodium chloride and the like may be added, as well as scouringabrasives, such as diatomaceous earth, ground pumice, bentonite, andvarious other clay and clay-like substances. In addition to the above,soil anti-redeposition agents such as carboxymethyl cellulose,cyanoethylated starches, and the like may be employed. The amount ofsuch special purpose additives will naturally vary within wide limits ormay even be omitted entirely. However, it has been found that amounts offrom about 1% up to as high as 80% by weight based on the formulationWeight may be added, depending upon the purpose for which theformulation is intended. Other additives which may be included aregermicides, fungicides, bactericides, odorants, colorants, brighteners,and the like.

In liquid detergent formulations, the detergent and the softener willnormally be present within the ranges specified above, as is true in thecase of bar detergent formulations and detergent formulations employingsolvents or the type normally used in dry cleaning.

Aqueous solutions of the softener may be prepared containing as much as50% or more of active material, though normally solutions containingfrom 3% up to are employed. When the softener solution is preparedindependently of the detergent formulation, it may be added convenientlyinto most cleaning devices, as for example automatic home washers andthe like.

As noted, the process and compositions of this invention are useful inhome, institutional and commercial laundering operations. This is so inthat the resetting of an automatic home washing machine to the finalrinse cycle for the addition of the present commercial softeners is notonly time-consuming, laborious, costly with respect to usage ofadditional hot water, but is also most inconvenient. It is advantageousto the user of an automatic home washer to use a softener with thedetergent, either anionic or non-ionic, and thus eliminate the need forresetting the machine for an additional final rinse cycle wherein thesoftener is added. In coin-operated washing machine establishments suchadditional rinsing requires additional financial charges whichdiscourage the use of a softener.

As has been described, the most convenient method of employing thesoftener solutions of this invention is in the wash cycle of theautomatic washer, along with the detergent, bleach and other additives.For this use, typically a 6-12% solution of the softener as its acidsalt is conveniently employed using one or two ounces of such solutionsdepending upon the size of the load of textile materials and the degreeof softening desired. The softener is added to the wash liquor alongwith the anionic or nonionic detergent, bleach, water softener, blueing,etc. and the normal cycles of washing, rinsing, spin-drying arecompleted. Drying the washed textiles may be accomplished in electric orgas dryers or by air drying on a clothes line. The dried textiles willpossess not only a high degree of softness but also will retain theirnatural water absorbency. Ironing of the textiles when necessary can beaccomplished without adverse effect on the softness imparted. Nodiscoloration of the textile will result from the use of the softener,either before or after ironing in the normal manner. It has been foundthat ironing is improved by the use of the softener in that the ironglides more easily on the treated textile, also less ironing isrequired. The softener will not interfere with the cleaning action ofthe detergent or specific action of other washing additives.

Certain automatic washing machines are equipped with a container towhich the softener may be added at the beginning of the wash cycle andwhich automatically dispenses the softener during the final rinse cycle.The softener of this invention may be added to such a container, ifdesired, or the softener may be added manually to the final rinse cycle,if so desired, without detracting from the utility of the softener.

When some modification of the property of textiles in addition tosoftening is desired and the compounds producing such effects are notcompatible with the wash liquor, use of the softener of this inventionin the wash liquor with the detergent will free the built-in dispenseror final rinse cycle for the addition of the desired compounds. Thus,certain compounds, e.g., germicides, water repellents, etc. notcompatible with anionic detergents, bleaches, etc. may now be added inthe final rinse cycle by the automatic dispenser or manually while thesoftener has already been added to the detergent wash liquor.

In order that the present invention may be more fully understood, thefollowing examples are given primarily by way of illustration. Nospecific details or enumerations contained therein should be construedas limitations on the present invention except insofar as they appear inthe appended claims. All parts and percentages are by weight unlessotherwise specifically designated.

In the following examples, Softeners A, B, C and D are commerciallyavailable softeners of the type employed in either home or commerciallaundering operations. Softener E is a softener of this invention. Theseare identified as follows:

AAn aqueous dispersion of approximately 6% solids of a quaternaryammonium softener containing at least one long chain aliphatic group.

BAn aqueous dispersion of approximately 6% solids of a quaternaryammonium softener containing at least one long chain aliphatic group.

CAn aqueous dispersion of approximately solids of a quaternary ammoniumsoftener containing two long chain aliphatic groups diluted to 6% solidsfor study.

D-A urea-adduct of a quaternary ammonium softener containing one longchain aliphatic group in which the softener is present to approximately20% of the total.

E-An acid salt of a preparation of 1,3-bis 2-(2-heptadecyl-l-imidazolinyl)ethyl biuret made in accordance with thisinvention.

A Kenmore automatic washing machine was used for all trials, employingthe hot wash-warm rinse setting, the regular wash cycle, and the lowwater level. A total of six white cotton bath towels comprised a washerload and weighed approximately three pounds or 1360 grams. Since thewashing machine contained approximately 9 gallons (34,000 grams) ofwater, the liquor to cloth ratio was approximately 25 to l. Acommercially available detergent composition containing sodiumdodecylbenzene sulfonate was used in all cases, at 18 grams per washload.

The towels were washed as described in the examples employing thecomplete washer cycle consisting of washing, rinsing, and spin-drying.In some cases, the final rinse cycle and spin-drying cycle wererepeated. The towels were then dried in a Kenmore electric dryer for 40minutes employing the hot setting and regular cycle. At the end of thefirst cycle of washing and drying, a towel was removed, properlyidentified, and held for comparison purposes. It was replaced by a freshtowel of identical construction and the complete Washing and dryingcycles repeated. This procedure was repeated so that two towels 8Results show Softeners A, C and Ball imparted improved softness to thewashed towels when the softeners were added to the final rinse cycle.However, only Softener E imparted both softness and instantaneousabsorbent in the load had received a total of ten washing and dryingproperties. cycles, the others having been removed after 1, 3, 5 and 7EXAMPLE 3 cycles and replaced by fresh towels. Thus, a total of ten Anexperiment was run according to the procedure of towels were involved ineach softener evaluation, four of Example 1 in which the Softeneremployed was the ace, which were replacements and not consideredfurther. tate Salt of Softener E a 6% Solution of PH 4.6 Highly Thesoftness of laumlered Was rated by a desirable softening without changein absorbency was obpanel of udges experienced in such rating, and theresults tamed on the Washed towe1s recorded are the averages of theratings by individual judgee EXAMPLE 4 Absorbency tests were run yPlacing a i of wfjlter Example 3 was repeated employing two acetate salton the pile surface of the towel and determining the time Solutions f Sft B, one as a solution or i required for complete disappearance of thewater drop Sien f pH 5 the other f PH y absorbence Withln the F T Values?P are Both products produced identical results which were the averagesof several determinations upon a single towel. equal to those obtainedin Example 3 EXAMPLE 1 2O EXAMPLE 5 Washing Operations were Carried onfour i of Example 3 was repeated employing the sulfate salt of towelsusing the amounts of softener in the wash liquor S ft E, the PH f theSolution being 2 5 Results as shown in Table I. Another set of towelswere washed equal to those reported in Example 3 were obtained. in thesame manner except that no softener was employed. EXA LE 6 The resultsare shown in Table l. MP

Softeners A, B, D and E were evaluated individually TABLE I in detergentwashing baths wherein swatches of various types of textile fabricsconstituted the washer load. Each Softener Used softness Ratings washerload consisted of the following:

Grams Kind Amount, 1 Wash 5 Washes 10 Washes COUCH percale 570Resin-finished cotton percale 1140 None Standard Standard---" Standard.Cotton Poplin 450 A Equal. Spun nylon 575 gg- Spun polyester 560 Muchsofter. Total 3295 6% stock solution of phosphoric acid saltpH of 5.0.The fun level of a Kenmore Washer was employed 6 ,56 n t Results showthat under these conditions of applica- 40 %z fgf g gfgg g fii ws ggfifi 21: i 2i tion of softengs. in i ilquor 5 i only a The regular washcycle and the hot wash-warm rinse setsoftener of this invention iseffective in imparting softtings were used. The cloth Swatches after aWash Cy C16 s E a both Oftness and bsorbenc were dried in a Kenmoreelectric dryer for 40 minutes n y 0 Her g Va 8 a at the hot setting andregular cycle. At the end of each EXAMPLE 2 complete wash and dry cycle,a sample of each fabric The experiments given in Example 1 were repeatedeX- Z l g q for f fg replaqed b a i cept that the softener was (in eachcase) added in an adno is t to maintain cons an ditional final rinsecycle, i.e., the regular wash cycle' emcompolslltlondan g f h 1 dploying 18 grams of a commercially available detergent sue f a1} a eswas F were emp oye composition containing sodium dodecylbenzenesulfonate to eva uatet e o owmv our so tenets was run followed by thenormal rinse and spin-dry cycles, Softeners used after which the machinewas reset to the final rinse cycle Kind: Amount, 100%, g. in which thesoftener was added and the machine allowed A 3.36 to complete theadditional phases of the normal cycle. The B 3.36 results of softnessand absorbency obtained are given in D 3.36 Table II. E (as thephosphate) 3.36

TABLE II Soft- Softness Ratings (No. of washes) ener Used NoneStandard-.- Standard Standard Standard-.- Standard. A Much softer. Muchsoiter Much softer..- Much softer.-. Much softer. C do -do do do Do. DEqii'il qiml Equal Equal EquaL E--- Much softer-.. Much softer.-- Muchsofter-.. Much softer". Much softer.

Absorbency Ratings-N0. of Washes (Wetting time in Seconds) None 0 0 0 00 A--- 0 0 i 3 5 0 1 3 5 10 D 0 0 o 0 0 E 0 0 0 0 0 0Instantaneous.

The above mentioned softeners were evaluated in the wash cycle employing36 grams of a commercially available anionic detergent compositioncontaining sodium dodecylbenzene sulfonate. After completion of thewashing and drying cycles, the cloth swatches were evaluated 5 thismannerfor softness and absorbency as aforementioned. Results are seen inTable HI.

EXAMPLE 7 Example 6 was repeated as described except that the TABLE IIISoftness Ratings Absorbency Ratings No. of Washes (Wetting time, sec.)

COTTON PERCALE Softener:

None Standard Standard 0 0 A goal Equal 1 10 30 B dn do 1 5 15 D .do do0 1 5 E Much softer... Much soften.-- 0 0 0 COTTON POPLIN Softener.

N one Standard Standard 0 0 0 A qual Equal. 2 15 30 B ..do do 2 30 D dndn 0 1 5 E Much soften.-. Much softer..- 0 0 0 BESIN-FINISEED COTTONPERCALE Softener: Nnne Standard Standard A S1. Softer Sl. Softer B EqualEqual D de .-dn E Much softer--. Much softer--.

SPUN NYLON Softener:

None Standard A- Much softer. B Sl. softer D ..do o E Much softer--.Much softer.--

SPUN' POLYESTER Softener:

None Standard Standard A-. Much softer.-- Much soften.-. B S1. softerSl. softer D ....do do E Much softer--- Much softer-.-

0-Instantaneous.

Results show that the imidazoline softener used is 50 softeners wereadded in an additional rinse cycle after equally effective on all fabrictypes tested when employed with anionic detergent in the wash cycle ofan automatic home washing machine. The commercial softeners availablefor use with automatic home washers and used in these trials were noteffective as softeners for cellulosic fabrics when employed in the washcycle with anionic completion of the regular wash, rinse and spin-drycycles With a commercially available anionic detergent compositioncontaining sodium dodecylbenzene sulfonate employed in the wash cycle.Softener E was employed as 55 the phosphate salt.

Results are seen in Table IV.

TABLE IV Softness Ratings Absorbency Ratings No. of Washes COTTONPERCALE Softener:

N one Standard Standard Standard 0 0 0 Much softer--. Much softer-.-Much softer-.- 5 25 30 Sl. softer S1. softer Sl. softer 2 30 V. 51.soften.-. V. sl. softer V. 51. soften... 0 2 30 Much softer--. Muchsofter--- Much softer... 0 0 0 corrou POPLIN Softener:

Standard Standard Standard 0 0 0 Much softer--- Much softer..- Muchsofter... 10 30 30 S1. softer S1. softer S1. softer 5 V. sl. soften--.V. sl. soften.-- V. 51. soften... 0 5 30 Much softer.-- Much softer-..Much softer.-. 0 0 0 TABLE IVCntinued Softness Ratings AbsorbencyRatings No. of Washes RESIN'FINISHED COTTON PERCALE Standard StandardStandard Much softer-.. Much softer-.. Much softer. S1. softer S1.softer Sl. softer- V. s1. soften--. V. s1. soften... V. s1. softe Muchsofter-.. Much softer.-. Much softe Standard Standard Standard Muchsofter Much softer- S1. softer-- S1. soften--- S1. softer-. S1.soften--- Much softe Much softer.-. Much softer-..

SPUN POLYESTER Softener:

Standard Standard Standard Much softer--. Much softer... Much softer-Sl. softer S1. softer S1. softer--. S1. softer S1. softer S1. softer...Much softer... Much softer... Much softer.-.

OInstantaneous.

Results indicate that the imidazoline softener is equiv- Results areshown in Table V. alent to the best of the commercial softeners used inTABLE V softness imparted to all fabric types, without adverse effect onabsorbency. Percent Percent Return 1 Soil EXAMPLE -8 Plckup 2 Twoswatches of standard soiled fabric were cut 4" Swatches washedinacomrnercially available anionic detergent colnpsoition containingsquare. Two swatches of the same fabric unsoiled were. Sodiumdodecylbomem sunonate only 0 10.6 269 also cut to the same size. Fourreflectance measurements Swatches washed in a commercially availableanionic detergent composition containing were run on each sample at 455m in different areas and 40 Sodium dodecylbenmne sulfontate p1 us aaveraged. One soiled and one unsoiled swatch were placed softener ofthis invention 15. 2 1. 05 in each of two Launder-Ometer jars, each jarcontaining ten stainless steel balls of one-quarter inch diameter. Inortlie soiled fabric. one jar was placed 200 ml. of a 0.25% solution ofa ulsoledmbnm commercially available anionic detergent composition con-Results show that the use of the imidazoline type softtaining sodiumdodecylbenzene sulfonate. In the other ener of this invention when usedin the wash cycle of an jar was placed 200 ml. of a 0.25% solution ofthe same detergent also containing 0.75 ml./liter of a 6% solution ofthe imidazoline softener as the phosphate salt. (This amount of softenercorresponds to the amounts recommended for use in the wash cycle of anautomatic washer containing a full load of fabric. The closed jars wereplaced in a Launder-Orneter and allowed to agitate for 12 minutes at 130F. after preheating. The liquor was then replaced with clean water at130 F. and the jars were allowed to agitate for an additional threeminutes. The swatches were then removed, squeezed to remove excessliquor, and allowed to dry on a clothes line at room temperature.

Reflectances were determined as before and averaged. Soil removal fromthe soiled fabrics and soil pick-up by the unsoiled fabric were thencalculated by the procedure given below.

Percent return to origional reflectance= X 100 Percent soil pickup= R X100 R ==refiectance of original cloth before soiling R =reflectance oforiginal cloth after washing automatic washing machine wherein anionicdetergent is present does not interfere with the cleaning action anddirt suspending properties of such detergents. The results actuallyindicate increased efficiency in both effects by the detergent in thepresence of the softener and is an unobvious advantage of the softenerof this invention.

EXAMPLE 9 A preparation of the imidazoline type of softener from behenicacid, diethylenetriamine and urea in which the desired ingredient hadthe structure EXAMPLE 10 A preparation of the imidazoline type ofsoftener from behenic acid, triethylenetetramine and urea having as thedesired component a compound of the structure 13 was evaluated inaccordance with the procedure of Example 1 as the acetate salt.

Excellent softness properties were obtained without change in absorbencyof the washed towels.

EXAMPLE 1 1 A preparation of the imidazoline type of softener from oleicacid, diethylenetriamine and urea having as the desired component acompound of the structure I Has was evaluated in accordance with theprocedure of Example 1 as the acetate salt.

Excellent softness properties were obtained without change in absorbencyof the washed towels.

EXAMPLE 12 A preparation of the imidazoline type of softener fromstearic acid and diethylenetriamine was crosslinked with thioureainstead of urea to give a product which had as the desired component acompound of the following struc- The product was evaluated according tothe procedure of Example 1 as the acetate salt.

Excellent softness was obtained without change in absorbency of thewashed towels.

EXAMPLE 13 EXAMPLE 14 A preparation of the imidazoline type of softenerfrom stearic acid and diethylenetriamine was crosslinked with double thenormal amount of urea to give a product having as the desired componenta compound of the structure shown in Example 13. The properties obtainedwith the softener when evaluated as the acetate in accordance with theprocedure of Example 1 were the same as those given in Example 13.

EXAMPLE 15 Softener E was evaluated according to the procedure ofExample 1 as the following acid salts- Acid:

Citric Sulfamic Oxalic Formic Tartaric Succinic p-Toluenesulfonicp-Toluenesulfonic Lactic Ratio (acid to softener) 2:1

14 Acid: Ratio (acid to softener) Lactic 1:1 Propionic 2:1 Propionic I1:1

In all cases good softness without change in absorbency of the washedtowels was obtained. However, the citric acid salt produced greatersoftness than the other acid salts.

EXAMPLE 16 A softener preparation was made employing stearic acid anddiethylenetriamine and removing only about 1.7 moles of water during thereaction followed by normal crosslinking with urea to yield a product ofthe following structure, which is of an amide condensate, not animidazoline.

The product was evaluated as the acetate salt according to the procedureof Example 1. No softness nor change in absorbency was obtained on thewashed towels.

EXAMPLE 17 A preparation similar to that of Example 16 was madeemploying behenic acid and diethylenetriamine to give a product of thefollowing structure, which is of an amide codensate, not an imidazoline.

Cis sa 0\ O=CNCHzOH:NCHzCHaNi-NH I I t The product was evaluatedaccording to the procedure of Example 1 as the acetate salt. No softnessnor change in absorbency was obtained on the washed towels.

EXAMPLE 18 The products of Examples 16 and 17 were evaluated accordingto the process of Example 2, that is, they were added in the final rinsecycle in the absence of detergent. Good softness properties wereobtained with some loss of absorbency on the washed towels.

The results of Examples 16, 17 and 18 show that only the imidazolinetype of softener of this invention is effective in a detergentcomposition while the amide condensates are effective in the absence ofdetergent, in the final rinse cycle.

EXAMPLE 19 A preparation of the imidazoline type of softener fromstearamide and diethylenetriamine crosslinked, without the usual ageingprior to crosslinking, with the normal amount of urea and having as thedesired component a compound having a structure similar to Softener Ewas evaluated as the acetate salt according to the procedure ofExample 1. Excellent softness without change in absorbency of the washedtowels was obtained.

EXAMPLE 20 A preparation similar to that of Example 19 was made frombehenamide and diethylenetriamine and had as the desired component acompound of the structure shown in Example 9. The product was evaluatedaccording to the procedure of Example 1, as the acetate salt. Excellentsoftness properties were obtained without change of absorbency of thewashed towels.

EXAMPLE 21 Softener E as the acetate salt was evaluated according to theprocedure of Example 1 except that a commercially available non-ionicdetergent composition containing an ethylene oxide condensate of talloil acids was employed instead of the anionic detergent composition.Good softness properties without loss of absorbency of the washed towelswere obtained.

15 1% EXAMPLE 22 5. A process for cleaning textile materials which com-Softener E was prepared as the citrate salt in solid prises having Pduring the cleaning Operation in all form. 7.9 grams of this solidproduct were mixed with amount sufficient to Produce a Softening effecton the 18 grams of the commercially available anionic detergent teXtilematafials Cleaned thBIEWi'Eh, Of an acid Salt of 3 containing sodiumdodecylbenzene sulfonate. The mixture compound of the formula 11% R I t\A N N(CH2CH2NH\ C--NHO NHCH2CHz N N .I A ly A l CHg-CH3 v CHz-CH: wasthen used to wash towels according to the procedure wherein R is analkyl group of from 12 to 22 carbon of Example 1. Excellent softnessproperties were obatoms, inclusive, where x is selected from the grouptamed w thout loss of absorbency on the washed towels. nsigfing f 1 nd2, y is a mall integer of from 0 to What is cla med is: 15 3, and whereA is selected from the group consisting of 1. An anionic or non-ionicdetergent softener composi- O and tion which is effective not only toremove soil from textile materials but also to soften said materialscomprising a detergent selected from the group consisting of anionic andnon-ionic detergents and as a softener 6. A process for launderingtextile materials which comprises laundering the textile material in anaqueous medium containing a detergent selected from the group aneffective amount of an acid salt of a compound of consisting of anionicand non-ionic detergents and an the formula amount sufficient to producea softening effect on the i M N N- omCHrNH -G-NHG- NHCH2OHQ N I I A ly JI CH3CH1 CHg-CH2 wherein R is an alkyl group of from 12 to 22 carbontextile material laundered therewith of an acid salt of a atoms,inclusive, where x is selected from the group concompound of the formulasisting of 1 and 2, y is a small integer of from 0 to 3, wherein R is analkyl group of from 12 to 22 carbon and where A is selected from thegroup consisting of atoms, inclusive, where x is selected from the groupcon- 0 and S. sisting of 1 and 2, y is a small integer of from 0 to 3,

2. An anionic or non-ionic detergent softener composiand where A isselected from the group consisting of tion which is effective not onlyto remove soil from O and S. textile materials but also to soften saidmaterials compris- 7. A process according to claim 6 in which the aciding a detergent selected from the group consisting of salt softener ispresent with the detergent during the anionic and non-ionic detergentsand as a softener an h Stage" f i of an Salt of P 8. A process accordingto claim 6 in which the softener q w fl) y 3 is an acid salt of 1,3-his[2-(2-heptadecyl-l-imidazolinyl)- 3. An anionic or non-ionic detergentsoftener compos1- ethynbiuret Y i f l noctonly i 23 9. A processaccording to claim 6 in which the softener ma mm s u a so 0 so en Sal maena S 00 pnsma a is the acetic acid salt of1,3-bis]2-(2-heptadecyl1-imiddetergent selected from the groupconsisting of anionic and non-ionic detergents and as a softener aneffective amount of the acetic acid salt ofl,3-bis[2-(2-heptadecyll-imidazolinyl ethyl] biuret.

azolinyl) ethyl] biuret.

10. A process for laundering textile materials which compriseslaundering the textile material in an aqueous 4. An anionic or non-ionicdetergent softener composimedium containing from 00005 and 1% of adetergent tion which is effective not only to remove soil from Selectedfrom the group consisting of anionic and textile materials but also tosoften said materials comionic detergents and fT0111-0001% to 01% Of anacid Salt prising from 5 to 95 parts of a detergent selected from of acompound of the formula R T J t n N/ N CHzCH2NH CNH-G NHCHzCH2 N \N I IA 1y J; I CHg-CH2 CHz-CH1 the group consisting of anionic and non-ionicdetergents wherein R is an alkyl group of from 12 to 22 carbon and as asoftener from about 0.1 to about 20 part of atoms, inclusive, where x isselected from the group conan acid salt of a compound of the formulasisting of 1 and 2, y is a small integer of from 0 to 3,

r i t I M N/ N OH2CHzNH C-NHC /NHCH2CH2\ N \N l A ly A I I CHE-CH2CH2CHZ wherein R is an alkyl group of from 12 to 22 carbon atoms, andWhere A is selected from the group consisting of O inclusive, where x isselected from the group consisting and S. of 1 and 2, y is a smallinteger of from 0 to 3, and where 11. A process for laundering textilematerials which A is selected from the group consisting of O and S.comprises laundering the textile material in an aqueous 17 mediumcontaining from .0001% to .5% of a detergent selected from the groupconsisting of anionic and nonionic detergents and from .0001% to 0.1% ofan acid salt of 1,3-bis [2-(2-heptadecyl-1-imidazoliny1) ethyl] biuret.

12. A process for laundering textile materials which compriseslaundering the textile material in an aqueous medium containing from.0001% to .5% of a detergent selected from the group consisting ofanionic and non- 18 ionic detergents and from .O0()1% to 0.1% of theacetic acid salt of 1,3-bis[2-(Z-heptadecyl-l-imidazolinyl)ethyl]-biuret.

No references cited.

LEON D. ROSDOL, Primary Examiner.

SAMUEL H. BLECH, Examiner.

S. E. DARDEN, Assistant Examiner.

1. AN ANIONIC OR NON-IONIC DETERGENT SOFTENER COMPOSITION WHICH ISEFFECTIVE NOT ONLY TO REMOVE SOIL FROM TEXTILE MATERIALS BUT ALSO TOSOFTEN SAID MATERIALS COMPRISING A DETERGENT SELECTED FROM THE GROUPCONSISTING OF ANIONIC AND NON-IONIC DETERGENTS AND AS A SOFTENER ANEFFECTIVE AMOUNT OF AN ACID SALT OF A COMPOUND OF THE FORMULA